In-situ TEM investigations on the microstructural evolution of SiC fibers under ion irradiation: Amorphization and grain growth

SiC/SiC composites are attractive candidates for many nuclear systems. As reinforcements, SiC fibers are critical to the in-service performance of composites. In this work, the temperature effects on the irradiation-induced microstructural evolution of Cansas-III SiC fibers were investigated using in-situ transmission electron microscopy (TEM). With in-situ 800 keV Kr ion irradiation, at room temperature (RT) the SiC fiber experienced heterogeneous amorphization and became completely amorphous at ～2.6 dpa. Above the critical temperature of crystalline-to-amorphous (T_c), SiC fibers underwent a simultaneous process of carbon packet disappearance and nano-grain growth at 300 °C and 800 °C. Possible mechanisms were discussed.     

Microstructure response of Amosic-3 SiC/SiC composites under self-ion irradiation

Amosic-3 SiC/SiC composites were irradiated at 300 °C using 6 MeV Si ions to peak doses of 13 and 55 displacements per atom (dpa). The loss of amorphous carbon packets and the growth of SiC grains were simultaneously observed in Amosic-3 SiC fibers, using a combination of transmission electron microscopy (TEM) and Raman spectroscopy. A mechanism based on the grain growth theory was proposed to expound the relationship between the loss of carbon packets and the growth of SiC grains. Small and curved SiC grains can absorb surrounding carbon packets to grow themselves; at some point, these grains further grow at the expense of adjacent small SiC grains until their grain boundary became straight. TEM images were found to support the above mechanism.     

Microstructure evolution in Si+ ion irradiated and annealed Ti3SiC2 MAX phase

Ti₃SiC₂ samples were irradiated by a 6-MeV Si⁺ ion to a fluence of 2 $\times$ 10¹⁶ Si⁺ ions/cm² at 300°C followed by annealing at 900°C for 5 h. A transmission electron microscope was used to characterize microstructural evolution. The phase of Ti₃SiC₂ transformed from the hexagonal close-packed (HCP) to a face-centered cubic structure after irradiation. Hexagonal screw dislocation networks were identified at the deepest position of the irradiated area, which are the products of dislocations reactions. After annealing, the irradiated region has reverted to the original HCP structure. High-density cavities and stacking faults were formed along the basal planes. In addition, ripplocations have been observed in the irradiated region in the Ti₃SiC₂ sample after annealing. Our insights into the formation processes and corresponding mechanisms of these defect structures might be helpful in the material design of advanced irradiation tolerance materials.     

Addressing amorphization and transgranular fracture of B4C through Si doping and TiB2 microparticle reinforcing

Over the last two decades, many studies have contributed to improving our understanding of the brittle failure mechanisms of boron carbide and provided a road map for inhibiting the underlying mechanisms and improving the mechanical response of boron carbide. This paper provides a review of the design and processing approaches utilized to address the amorphization and transgranular fracture of boron carbide, which are mainly based on what we have found through 9 years of work in the field of boron carbides as armor ceramics.     

In-situ TEM study of Kr ion irradiation tolerance of SiFeOC nanocomposite

In this work, ion irradiation of polymer derived SiFeOC nanocomposite was carried out using 1.2 MeV Kr ions at room temperature and 600°C. The starting composite was composed of Fe₃Si, SiC, SiOC, SiO₂, and graphitic C. In-situ TEM investigations show uniform distribution of nano-crystalline Fe₃Si and SiC phases in the amorphous SiOC matrix. During ion irradiation, the SiOC bulk microstructure and interfaces between Fe₃Si or SiC crystallites and the SiOC matrix remain defect-free and demonstrate outstanding ion irradiation resistance. At room temperature, the crystalline domains are stable up to 2 dpa. At 600°C, Fe₃Si crystallites are more stable than SiC; SiC crystallites are stable up to 4 dpa while the Fe₃Si crystallites are stable up to 10 dpa. These crystallites also coalescence and amorphize simultaneously during ion irradiation. The exceptional tolerance to defect formation and irradiation of the SiFeOC nanocomposite provides important guidance to developing irradiation resistant fuels for advanced gas cooled reactors.     

Structural characterization,defect evolution and luminescence properties of natural CaF2 under 10 MeV electron irradiation

Present study investigates the response of various coloured variants of natural fluorite (CaF₂) to 10 MeV electron beam irradiation at accumulated dose of 5–10 MGy. The fluorite specimens did not show any post irradiation radioactivity. However, after irradiation the specimens developed purple colouration of different shades depending on the dose. In-depth characterization of the as-received and irradiated specimens using XPS and Raman spectroscopy confirm the relocation of fluorine (F) anions at interstitial sites and formation of metallic calcium (Ca). The calculated displacement cross sections for F and Ca indicate that it is easier to form fluorine anion interstitials within lattice structure. However, the estimated lower fraction of interstitial fluorine (∼14%) as compared to metallic Ca (>50%) is attributed to their surface diffusion and desorption. Electron irradiation was found to cause photoluminescence quenching in all the CaF₂ specimens that is likely caused by a radiation-induced formation of competing recombination channels.     

Damage microstructure evolution of helium ion irradiated SiC under fusion relevant temperatures

In-situ transmission electron microscopy (TEM) with ion irradiation has been used to study the damage microstructure evolution of He ion irradiated 4-H SiC at nuclear fusion relevant temperatures. The SiC samples were irradiated with 20?keV He ions at 25, 400, 800 and 1200?°C to a dose of 5.0 displacements per atom (DPA). At 25?°C, the material fully amorphises at 1.5 DPA and no He bubble nucleation occurs up to the doses studied. At 400 and 800?°C, He bubble nucleation occurs and the material remains crystalline. Bubble nucleation occurs at 2.0?DPA at 400?°C but occurs at only 0.5?DPA at 1200?°C. This is attributed the He atoms de-trapping from vacancies and migrating interstitially to larger He-vacancy clusters at higher temperatures, leading to faster nucleation of observable He bubbles. Helium platelets form at an irradiation temperature of 1200?°C at 0.5?DPA showing a preference for nucleation between the {0001} basal planes.     

硅/碳化硅材料用作电解铝热电偶保护管的可行性研究

本文研究了900℃碳化硅材料在气／冰晶石／铝液三相区介质的抗蚀情况。用扫描电镜和X衍射仪观察分析了试样在熔液区的界面形貌与物相组成。研究结果表明：碳化硅材料除在电解质／空气界面有较明显的侵蚀外。在熔融的冰晶石与铝液的混合介质中表现出良好的抗腐蚀能力,用作电解铝热电偶保护管有较好的应用前景。     

Ion beam irradiation of ABO4 compounds with the fergusonite,monazite, scheelite,and zircon structures

The effects of irradiation on CaWO₄, SrWO₄, BaWO₄, YVO₄, LaVO₄, YNbO₄, and LaNbO₄ were investigated on thin crystals using 1.0 MeV Kr ions at 50-1000 K. All of the ABO₄ compounds can be amorphized with calculated damage cross sections (σ_a = 1/F_c0) in the range of ~0.30-1.09 × 10^-14 cm² ion⁻¹ at zero Kelvin. The analysis of fluence-temperature data returned critical temperatures for amorphization (T_c) of 311 ± 1, 358 ± 90, 325 ± 19, 415 ± 17, 541 ± 6, 636 ± 26, and 1012 ± 1 K, respectively, for the compounds listed above. Compared with previous in situ irradiation of ABO₄ orthophosphate samples using 0.8 MeV Kr ions, the T_c values of LaVO₄ and YVO₄ are higher than those of LaPO₄ and YPO₄ by 82 K and 124 K, respectively. The T_c values of the three scheelite structures, CaWO₄, SrWO₄, and BaWO₄, indicate that they are the most radiation tolerant compounds under these conditions. The A-B cation anti-site energies, E_fAB, determined by DFT range from 2.48 to 10.58 eV and are highly correlated with the A-B cation ionic radius ratio, r_A/r_B, but are not correlated with T_c across the different structure types, suggesting that the formation and migration energies of Frenkel defects play a more important role in damage recovery in these compounds. We also discuss the role of cation and anion charge/iconicity as determined by DFT. ABO₄ compounds with the zircon structure and B = P or V have a distinct advantage over those with B = Si as the damaged regions do not appear to be significantly affected by polymerization of (PO₄)³⁻ or (VO₄)³⁻ groups which might stabilize the amorphous fraction and ultimately lead to phase separation as observed in zircon (ZrSiO₄).     

Comparative study of gamma and ion beam irradiation of polymeric nanocomposite on electrical conductivity

Poly(vinyl alcohol) (PVA) was used to prepare nanocomposites of multi‐wall carbon nanotubes (MWCNT) and functionalized carbon nanotubes (MWCNT‐NH₂) in existence of 2‐carboxyethyl acrylate oligomers (CEA). Radiation‐induced crosslinking of the prepared matrix was carried out via gamma and ion beam irradiation. A comparative study of gamma and ion beam irradiation effect on the electrical conductivity of nanocomposite was conducted. The gelation of the gamma irradiated matrix outperforms the ion beam irradiated matrix. The order of gelation is PVA > (PVA/CEA) > (PVA/CEA)‐MWCNT > (PVA/CEA)‐MWCNT‐NH₂. There is a significant reduction in the swelling of the nanocomposite. The formation of nanocomposites was confirmed by scanning electron microscopy, energy‐dispersive X‐ray (EDX) and FTIR examinations. The direct current electrical properties of PVA/nanocomposites are examined at room temperature by applying electric voltage from 1 to 20 V. The results revealed that the electrical conductivity is increased by adding the carbon nanotubes and irradiation by gamma and ion beam. At an applied electric voltage 20 V, in the electrical conductivity of the unirradiated PVA was from 9.20 × 10^?8 S cm^?1. After adding MWCNT an increase up to 4.70 × 10^?5 S cm^?1 was observed. While after ion beam irradiation, a further increase up to 9.30 × 10^?5 S cm^?1 was noticed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46146.     

Transmission electron microscopy of supported molybdenum and vanadium oxides

Transmission electron microscopy has been used to characterize dispersions of molybdena and vanadia on titania and silica supports. When silica spheres of controlled morphology were used as support, the dispersed monolayer phase of both oxides could be imaged due to characteristic changes in contrast. In addition to the dispersed phase, we could detect three-dimensional crystallites of V₂O₅ but in the case of MoO₃ only two-dimensional islands were seen. On Degussa P-25 titania, there was no observable contrast change due to the presence of a monolayer of these dispersed oxides. However, exposure to the electron beam caused dramatic changes in the surface texture of the support. Such changes were not seen when blank TiO₂ was similarly irradiated. These e-beam induced changes were more pronounced in the vanadia/titania catalysts leading to formation of 1–3 nm clusters of reduced VO _x . However, on the MoO₃/TiO₂ sample, e-beam exposure caused only a pronounced change in texture but no well defined clusters could be detected.     

Structural study of β‐SiC(001) films on Si(001) by laser chemical vapor deposition

β‐SiC thin films have been epitaxially grown on Si(001) substrates by laser chemical vapor deposition. The epitaxial relationship was β‐SiC(001){111}//Si(001){111}, and multiple twins {111} planes were identified. The maximum deposition rate was 23.6 μm/h, which is 5‐200 times higher than that of conventional chemical vapor deposition methods. The density of twins increased with increasing β‐SiC thickness. The cross section of the films exhibited a columnar structure, containing twins at {111} planes that were tilted 15.8° to the surface of substrate. The growth mechanism of the films was discussed.     

Irradiation response of Al2O3-ZrO2 ceramic composite under He ion irradiation

The dense Al₂O₃-ZrO₂ ceramic composite prepared by spark plasma sintering was irradiated by 500 keV He ions with different fluences and temperatures. The microstructural evolution and mechanical properties were investigated. The results showed that peak broadening and shifts at RT revealed by GIXRD and Raman are associated with damage induced microstrain and formation of point defects. The recovery at 500 °C suggested the reduction of irradiation induced damage. Compared with α-Al₂O₃, t-ZrO₂ exhibited a reverse trend in lattice parameters change and lattice expansion. Many helium bubbles with oblate and ribbon-like shape were mainly formed in α-Al₂O₃ grains at He concentration peak at 1.0 × 10¹⁷ ions/cm². With increasing of fluence at RT, ribbon-like helium bubbles developed into microcracks at 4.0 × 10¹⁷ ions/cm². Though evident structural changes, no full amorphization was observed at 4.0 × 10¹⁷ ions/cm². Formation of ribbon-like bubbles and microcracks is the main mechanism for degradation of mechanical properties of irradiated Al₂O₃-ZrO₂ composite.     

Micromechanical properties and microstructural evolution of Amosic-3 SiC/SiC composites irradiated by silicon ions

In this work, Amosic-3 SiC/SiC composites were irradiated to 10 dpa and 115 dpa with 300 keV Si ions at 300 °C. To evaluate its irradiation behaviour and investigate the underlying mechanism, nanoindentation, AFM, Raman and electron microscopy were utilized. Nanoindentation showed that although micromechanical properties declined after irradiation, hardness and Young’s modulus were maintained better under 115 dpa. AFM manifested differential swelling among PyC interface, fiber and matrix and SEM showed irradiation-induced partial interface debonding, which are both more obvious under 115 dpa. TEM revealed the generation and proliferation of amorphous regions, which is according with the decline and broadening of peaks in Raman spectra. The material was almost completely amorphous after irradiated to 10 dpa while recrystallization occurred under 115 dpa. All results mentioned above contribute to the decline of hardness and Young’s modulus and may explain why the micromechanical degradation was more significant under 10 dpa.     

Reduction study of Co3O4 model catalyst by electron microscopy

Evolution of microstructure and morphology of Co₃O₄ particles in the model systems during reduction in hydrogen was studied by transmission electron microscopy methods. Based on SAED and HRTEM results we found that the degree of reduction of Co₃O₄ strongly depends on the particle size and morphology, which are determined by the pretreatment conditions. Preferential epitaxial growth of CoO and Co phases on Co₃O₄ during reduction was deduced from HRTEM images.     

Activated combustion of a silicon—carbon mixture in nitrogen and SHS of Si3N4—SiC composite ceramic powders and silicon carbide

It is established that Si₃N₄—SiC composites with a mass content of SiC 5–60% and a dominating content of the β-modification of silicon nitride can be produced by interaction of the components in the Si—C—N₂ system in the combustion regime. It is found that the fraction of α-Si₃N₄ can be increased by diluting the starting mixture with the end products, but this leads to the occurrence of a certain amount of unreacted silicon in the products. It is shown that the use of chemical activation allows one to perform a single-stage synthesis of Si₃N₄—SiC composites with any contents of the individual components (from 0 to 100%), including pure carbide silicon. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 5, pp. 56–62, September–October, 2006.     

In situ Growth of SiC Whisker in Pyrolyzed Monolithic Mixture of AHPCS and SiC

In situ whisker growth was observed during heat treatment of allylhydridopolycarbosilane (AHPCS) and SiC powder in the temperature range of 1250°–1350°C. TEM equipped with an electron energy loss spectrometer (EELS) verified that the banded whiskers are twinned single-grained β-SiC. Convergent beam electron diffraction patterns (CBED) of the whisker tips were consistent with formation by a vapor–solid (VS) mechanism. The effects of process variables on whisker growth were addressed. The mechanism of whisker growth was discussed and attributed to the reaction between the gaseous products of the polymers AHPCS and polycarbosilane (PCS). Thermal decomposition behavior of the polymers was followed to relate gas evolution to whisker formation.     

Effect of additives on slip casting rheology,microstructure and mechanical properties of Si3N4/SiC composites

The SiC/Si₃N₄ composites were fabricated with sintering process. To produce SiC/Si₃N₄ composite components, slurry mixtures containing Si/SiC powders were used by the slip casting method. In order to investigate the effect of dispersants and additives on the rheological properties and the body casted, slurries with concentration of 70% solid weight were prepared. It included a mixture of silicon and silicon carbide with weight ratios of 30 wt% and 70 wt%, respectively, and various weight percentages of Ball clay as lubricant and Tiron (sodium salt of benzene disulfonic acid) as dispersant at pH value of 7. After preparing the green bodies by slip casting method by using plaster mold, the samples were sintered at 1450 °C inside an atmospheric-controlled furnace under a pressure of 0.12 MPa of nitrogen gas for 2 h. By examining the rheological properties of the slurry and the sintering properties, it was concluded that the best slurry was obtained in terms of viscosity, density, porosity and strength using 5 wt% Ball clay and 0.5 wt% Tiron. Phase transformations, microstructure and morphology of the sintered specimens were accomplished by Field Emission Scanning Electron Microscopy (FESEM) examination and X-ray diffraction experimental analysis. XRD and FESEM results demonstrated that the composite fabricated by slurry containing 5 wt% Ball clay and 0.5 wt% Tiron had the least porosity without SiO₂ phase.     

Atomic order-disorder engineering in the La2Zr2O7 pyrochlore under low energy ion irradiation

Cation and anion disordering affect the structural and electronic properties of the isometric A₂B₂O₇ pyrochlore materials. Here, we report a study on the structural response of La₂Zr₂O₇ at two different temperatures (300 K and ~88 K) as a function of ion fluence (1 × 10¹³, 5 × 10¹³, and 1 × 10¹⁴ ions/cm²). The effect of ion fluence and irradiation temperature on the structural properties have been investigated using the grazing angle x-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy. GIXRD results confirmed that the weakening/broadening of the diffraction peaks and lattice volume expansion increases monotonically as a function of ion fluence at both the temperatures and are more pronounced at ~88 K. The cation and anion disordering appear to be ion fluence and irradiation temperature-dependent. Raman spectroscopy shows that the atomic disordering is more pronounced with enhanced ion fluence and revealed the involvement of the X_48f parameter in the enhancement of disordering in the system. The HRTEM analysis revealed that the deterioration in the atomic ordering (amorphization) is significantly more pronounced at ~88 K. The qualitative analysis of cation/anion disordering and structural deformation revealed that irradiation parameters play a crucial role in developing and altering the properties of the pyrochlore materials for the technological applications.     

SiO2加入量对Si2N2O结合SiC试样相组成与显微结构的影响

以纯度均>97%的磨料级黑SiC、硅粉和SiO2粉为原料,加入临时结合剂,混练15~20 min后,在油压机上压成125 mm×25 mm×25 mm的试样,再将干燥后的生坯在高纯氮气中于1 450℃10 h氮化烧成后,制成了SiO2加入量(w)分别为0、4%、6%、8%、10%的Si2N2O结合SiC试样,以研究SiO2加入量对材料相组成与显微结构的影响。结果表明:随着SiO2细粉加入量的增加,试样基质中的Si2N2O生成量逐渐增加,Si3N4量逐渐降低;试样的整体结构变得越来越致密,孔洞部位Si2N2O晶体的发育越来越趋于完全。